Container of a malodorous warning liquid for malfunctioning mine ventilation

ABSTRACT

THE MALODOROUS WARNING COMPOSITION OF MATTER INCLUDES THE INGREDIENTS OF A LIQUID MERCAPTAN MIXED WITH A NONFLAMMABLE SOLVENT HAVING A RELATIVELY LOW VAPOR PRESSURE, SUCH AS TRICHLOROMONOFLUOROMETHANE, AND AN INERT GAS SUCH AS NITROGEN UNDER PRESSURE, TO FORM A MALODOROUS MIXTURE FOR INTRODUCTION INTO PRESSURIZED AIR BREATHING SYSTEMS, SUCH AS FOR MINES, TO WARN A PERSON OF DANGER BY THE ODOR. THIS NEW COMPOSITION OF MATTER HAS NO NEED FOR EXTERNAL MEANS OF HEATING OR COOLING THE MIXTURE FOR INTRODUCING IT INTO THE PRESSURIZED AIRE BREATHING SYSTEM. THE PROCESS FOR ITS PREPARATION INCLUDES THE STEPS OF INTRODUCING AN INERT GAS UNDER PRESSURE INTO A SUITABLE CONTAINER IN WHICH THE MERCAPTAN AND SOLVENT HAVE BEEN PREVIOUSLY PLACED, AND PRODUCING A PRESSURE INTERNALLY OF ABOUT 250 TO 300 POUNDS PER SQUARE INCH, AND SEALING THE CONTAINER BY A NEEDLE VALVE OR OTHER SUITABLE MEANS.   THE WARNING DEVICE INCLUDES THE MALODOROUS COMPOSITION OF MATTER TOGETHER WITH A SUITABLE HIGH PRESSURE CONTAINER EQUIPPED WITH A HIGH PRESSURE NEEDLE VALVE. THE WARNING SYSTEM INCLUDES THE WARNING DEVICE TOGETHER WITH AN ADAPTER ON THE END OF THE NEEDLE VALVE, TO WHICH IS CONNECTED A FEEDER TUBE MEANS HAVING A FITTING OR COUPLING FOR CONNECTION OF ITS OUTER END TO A VALVE OF ITS OUTER END TO A VALVE OF A PRESSURED AIR BREATHING SYSTEM OF A FACILTIY SUCH AS A MINE.

OCL 1973 A. B. SELLECK CONTAINER OF A MALODOROUS WARNING LIQUID FORMALFUNCTIONING MINE VENTILATION Filed July 23, 1971 f/vvEA/Tofie.

945527 B. SELLECK 3 9 H 99 IQTTO/QNEV- United States Patent 3,767,591CONTAINER OF A MALODOROUS WARNING LIQUID FOR MALFUNCIIONING MINEVENTILATION Albert B. Selleck, 19310 Caladero St., Tarzana, Calif. 91356Filed July 23, 1971, Ser. No. 165,537 Int. Cl. C09k 3/30 US. Cl. 252-4082 Claims ABSTRACT OF THE DISCLOSURE The malodorous warning compositionof matter includes the ingredients of a liquid mercaptan mixed with anonfiammable solvent having a relatively low vapor pressure, such astrichloromonofluoromethane, and an inert gas such as nitrogen underpressure, to form a malodorous mixture for introduction into pressurizedair breathing systems, such as for mines, to Warn a person of danger bythe odor. This new composition of matter has no need for external meansof heating or cooling the mixture for introducing it into thepressurized air breathing system.

The process for its preparation includes the steps of introducing aninert gas under pressure into a suitable container in which themercaptan and solvent have been previously placed, and producing apressure internally of about 250 to 300 pounds per square inch, andsealing the container by a needle valve or other suitable means.

The warning device includes the malodorous composition of mattertogether with a suitable high pressure container equipped with a highpressure needle valve. The warning system includes the Warning devicetogether with an adapter on the end of the needle valve, to which isconnected a feeder tube means having a fitting or coupling forconnection of its outer end to a valve of its outer end to a valve of apressured air breathing system of a facility such as a mine.

BACKGROUND OF THE INVENTION (1) Field of the invention This inventionrelates to a malodorous composition of matter for introduction into apressurized air breathing system, such as those used for mines, to warna person of danger by the malodorous smell. The process for itspreparation involves the mixing of a mercaptan with a nonflammablesolvent with a relatively low vapor pressure over a wide range oftemperatures and subjecting the resulting mixture with an inert gasunder pressure for expelling the composition of matter into apressurized air breathing system.

The invention also includes the combination of a malodorous compositionof matter with a suitable high pressure container equipped with a highpressure needle valve, to form a warning device. The invention alsoincludes a mine warning system when the warning device is equipped withan adapter connected to a tube means leading to a valve of a pressurizedair breathing system of the desired facility.

(2) Prior art Applicant knows of no prior art making use of theparticular combination of ingredients disclosed in this application, orof a process for its preparation as described herein, or of acombination of such ingredients together with a high pressure containerand needle valve, or additionally of an adapter and feeder tube means.

SUMMARY OF THE INVENTION The malodorous composition of matter has threebasic ingredient: a mercaptan, to produce the warning odor; a solventfor the mercaptan, which serves to reduce the 3,767,591 Patented Oct.23, 1973 flammability and explosive qualities of the mercaptan by actingas a diluent and nonflammable solvent medium; and an inert gas underpressure to force the composition of matter from a high pressurecontainer into the pressurized air breathing system. 7

For relative ease in preparing the malodorous composition of matter, aliquid mercaptan at ambient temperatures is preferred. Such mercaptansinclude methyl mercaptan, ethyl mercaptan, both n-propyl and iso-propylmercaptan, referred to hereinafter as propyl mercaptan, both secondaryand tertiary butyl mercaptan, both referred to hereinafter as butylmercaptan, and tetrahydrothiophene, referred to hereinafter asthiophane.

Other suitable malodorous compounds for this composition of matterinclude dimethyl sulfide, and ethyl iso-propyl sulfide.

Since all of these compounds are flammable or explosive or both, it ishighly desirable to incorporate them into a nonfiammable solvent forsafety and ease in handling and application. Such a solvent must alsohave a relatively low vapor pressure over a relatively wide temperaturerange, which may be defined as a maximum vapor pressure of not over 40pounds per square inch at 1 atmosphere, i.e. sea level, at a maximumtemperature of degrees Fahrenheit. Such suitable solvents aretrichloromonofluoromethane, trichlorotrifluoroethane,1,1,l-trich'loroethane, also known as methylchloroform, methylenechloride, trichloroethylene, and perchloroethylene.

Since the vapor pressure at sea level of these solvents is lowered asthe temperature is decreased below the maximum temperature of 130degrees Fahrenheit, the only limitation as to cold temperatures is theelfectiveness of the inert gas under pressure to expel the compositionof matter from the container into the pressurized air breathing system.

The usual pressurized air breathing system for mines in the UnitedStates averages about pounds per square inch, With respect to the amountof pressure used. So long as the internal pressure in the containerholding the malodorous composition of matter exceeds 150 pounds persquare inch, no difiiculty exists in using the warning mixture.

Nitrogen gas is a particularly suitable inert gas for use in preparingthe malodorous composition of matter. When the container has beencharged with nitrogen gas to an internal pressure of about 275 poundsper square inch at room temperatures, sufficient pressure exists toexpel the contents of the container at temperatures as low as 30 F. intopressurized air breathing systems maintained at a pressure of 150 poundsper square inch. Also, the increase in internal pressure of such acontainer, thus charged with nitrogen gas, at a temperature of 130 isinsufiicient to burst the standard high pressure cylinder used as acontainer for the malodorous composition of matter.

Various other inert gases having similar characteristics as nitrogen gasmay also be used. For example, carbon dioxide gas or nitrous oxide gasmay be used without adversely aifecting the results obtained by myinvention.

Once the malodorous composition of matter has been prepared under thedesired pressure in a high pressure container, the container may bestored for an indefinite period of time Without adversely affecting theoperation of my invention. Moreover, when the container is to beemployed, it may be used without any other preparation of heating orcooling of the contents, before introducing the contents into apressurized air breathing system.

The container is preferably a high pressure cylinder capable ofwithstanding up to 375 pounds per square inch pressure or more at sealevel, and equipped with a high pressure needle valve having a corrosionresistant seat of Teflon or other suitable material. The container andvalve,

3. together with the malodorous composition of matter, make up the minewarning device.

When the warning device is equipped further with an adapter andfeedertube means, for attachment to a valve of a pressurized airbreathing system for a facility such as a mine, the invention thenbecomes a warning system.

It is, therefore, an object of this invention to provide a malodorouswarning composition of matter which is relatively easy to prepare and tostore for long periods of time without deterioration or specialhandling.

Another object of this invention is to provide 21 malodorous warningcomposition of matter which can be contained in a high pressure cylinderand used immediately over a range of temperatures from about F. to about130 F. without the necessity for heating or cooling the container or itscontents.

A further object of this invention is to provide a malodorous warningcomposition of matter which can be prepared from readily availablematerials and at a relatively inexpensive cost.

A still further object of this invention is to provide a malodorouswarning composition of matter which is relatively safe to use both fromthe aspect of being relatively nontoxic and relatively nonflammable.

A yet another object of this invention is to provide a warning devicecapable of containing said malodorous composition of matter underpressure and of permitting said composition of matter to escape througha valve means.

A yet further object of this invention is to provide a warning systemhaving the capability of containing and delivering said malodorouscomposition of matter under pressure when desired into a pressurized airbreathing system of a facility such as a mine, over a range oftemperatures from about 10 F. to about 130 F., without the necessity forheating or cooling the container of the warning system or its contents.

These and other objects will be more readily understood by reference tothe following specification and claims, taken in conjunction with theaccompanying drawing, in which FIG. 1 is a side elevational view of theinvention in position for introducing the malodorous composition ofmatter into a pressurized air breathing system of a facility, said airbreathing system being shown in part and by dotted lines.

DESCRIPTION OF PREFERRED EMBODIMENTS The warning device 10 has a highpressure cylinder 12 with an internal capacity of about 75 cubic inches.One end of the cylinder 12 is equipped with a high pressure needle valve14 with a handle 15 to open and close the valve 14. Preferably, thevalve 14 is equipped with a corrosion resistant seat made of Teflon orother corrosion resistant material. An adapter 16 is attached to theouter end of the valve 14.

The malodorous warning composition of matter 18 included and containedin the warning device 10 occupies only part of the interior of thecylinder 12, the rest being taken up by the compressed inert gas 20.

Warning system 22 includes warning device 10 with malodorous compositionof matter 18 and compressed inert gas 20, together with feeder tube 24having a flared threaded fitting 26 connected to adapter 16 at one end,and having a similar flared threaded fitting 27 at its other endconnected to adapter 28 threaded on pipe nipple 29 of valve 30 openinginto the pressurized air breathing system 32 of the facility, shown inpart and by dotted lines in the drawing. Various alternative connectingmeans may be used.

The same general procedure is used in the preparation of the malodorouswarning composition of matter, regardless of the various ingredientsused in each of the three categories making up the malodorous warningcomposition of matter-the substance producing the warning 4, odor, thesolvent, and the inert gas. Although not essen? tial, I have found itpreferable to add an additional step in the preparation of themalodorous composition of matter of agitating the contents of thecontainer after being charged with the inert gas, and then re-chargingthe container to allow for a decrease in internal pressure due to thepartial absorption of the inert gas under pressure by the liquidcontents. In this matter, a uniform internal pressure may be achievedand maintained inside the container.

EXAMPLEl The preparation of the malodorous composition of matter may beaccomplished at ambient temperatures such as room temperature of about70 F. or at other convenient ambient temperatures.

About grams of ethyl mercaptan is placed inside a cylinder 12 capable ofwithstanding relatively high internal pressure such as 300 to 350 poundsper square iiich at sea level and equipped with a high pressure needlevalve 14. A suitable internal capacity of the cylinder is about 75 cubicinches.

Next, about 450 grams of solvent, trichloromonofluoromethane is added tothe 100 grams of ethyl mercaptan inside the cylinder.

Then, sufiicient nitrogen gas under pressure is introduced through theneedle valve 14 into the cylinder .12 to produce an internal pressure ofabout 275 pounds per square inch inside the cylinder 12 at ambient"temperatures.

Optionally, and preferably, the cylinder 12 is then agitated for aminimum period of time of about 30 seconds to mix the liquid contentsthoroughly inside the cylinder 12 and to complete whatever absorptionmay occur of the inert nitrogen gas by the mixture of ethyl mercaptanand trichloromonofluoromethane solvent. su'c'h absor'ption may vary from3 to 6 percent by weight of the nitro gen gas and may lower the initialinternal pressure of the cylinder 12 from about 275 pounds persquareinch" to about 240 to 245 pounds per square inch. Since siichlower pressures are more than ample for introduction of the malodorouscomposition of matter into conventional pressurized air breathingsystems of about pounds per square inch in the United States,rercharging of the cylinder 12 with nitrogen gas back up to the initialinternal pressure of about 275 pounds per square inch' is not actuallynecessary.

To maintain uniformity of pressure, however, additional nitrogen gasunder pressure is introduced through the needle valve 14 of the cylinder12 until the initial internal pressure of 275 pounds per square inch isrestored, as indicated by the pressure neutralization gauge -of anitrogen gas reservoir tank.

The needle valve 14 is then closed and capped with a safety cap forstorage purposes. The charged cylinder may then be stored as neededwithout any special precautions of locations or of ambient temperatures.

In the example given above, the amount of nitrogen gas by weight tomaintain an internal pressure of about 275 pounds per square inch afteragitation of the cylinder 12, is about 30 grams by weight at ambienttemperatures.

In use, the warning device 10 is placed in a vertical" position with itsneedle valve 14 at the bottom. The

safety cap (not shown), if on the needle valve 14, is

removed. Fitting 26 of feeder tube 24 is connected to the adapter 16 onthe outer end of the needle valve 14 and (fitting 27 on the other end offeeder tube 24 is connected;

substantial part of the inert gas 20 are exhausted into the pressurizedair breathing system 32 in about 5 seconds, until the remaining inertgas in the cylinder 12 reaches an equilibrium pressure with the pressureof the pressurized air breathing system 32.

Valve 30 of the pressurized air breathing system 32 is then closed, andthe warning system 22 is then removed from its connection with thepressurized air breathing system 32.

If desired, the cylinder 12 may be disposed of, or reused as part ofanother warning device and warning system 22. Due to the novel featuresof my invention, the warning system 22 is fully effective at ambienttemperatures ranging from a minimum of about 10 F. to about 130 F.without any heating or cooling of the cylinder 12, and without anyspecial preparation, where the pressurized air breathing system of themine or other facility is at a pressure of about 150 pounds per squareinch.

EXAMPLE 2 The steps of Example 1 are repeated with the substitution ofabout 100 grams of methyl mercaptan instead of ethyl mercaptan and thesame results are obtained.

EXAMPLE 3 The steps of Example 1 are repeated with the substitution ofabout 450 grams of trichlorotrifiuoroethane instead of thetrichloromonofiuoromethane and the same results are obtained.

EXAMPLE 4 The steps of Example 2 are repeated with the substitution ofabout 450 grams of trichlorotrifiuoroethane instead of thetrichloromonofluoromethane and the same results are obtained.

The ratio of parts by weight of the liquid malodorous substance and thesolvent may vary from 1 part of the former to 2 parts of the latter, asa maximum, to about 1 part of the former to about 6 parts of the latter,without adversely affecting the results. Also, the amount of inert gasmay vary from .2 to .4 parts by weight Where the ratio of liquidmalodorous substance and solvent is 1:2 and 1:6 respectively, therebyproducing a variance in internal pressure of a 75 cubic inch highpressure cylinder from about 200 pounds per square inch to about 430pounds per square inch at room temperatures of about 70 F. withoutadversely afiecting the results. Of course, for the higher pressures,suitable high pressure cylinders must be used that are capable ofwithstanding such higher pressures.

If it is desired to use high pressure cylinders of greater or lessercapacity than 75 cubic inches internally, the various amounts ofingredients can be adjusted in proportion to the increased or diminishedcapacity of the cylinder so that effective operating pressures may beobtained internally over the temperature range of 10 F. to 130 F. Thehigher internal pressures, i.e. over 275 pounds per square inch, may beelfectively used where the expected operating temperatures are below 30F. The only essential requirement for operation of my invention is thatthe internal pressure of the charged cylinder be in excess of thepressures used in the pressurized air breathing system of the particularfacility where the malodorous warning composition of matter is to beintroduced.

Although I have described preferred embodiments of my invention, it isunderstood that the scope of the invention is not limited thereby, butnumerous variations in ingredients and procedures are possible withoutdeparting from the spirit and scope of the invention as claimedhereinafter.

What is claimed is:

1. In combination, a high pressure closed container capable ofwithstanding internal pressure containing therein about 1 part by weightof a liquid malodorous substance selected from the group consisting ofmethyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan,thiophane, dimethyl sulfide, and ethyl iso-prop'yl sulfide, from about 2to 6 parts by weight of a nonflammable solvent for said liquidmalodorous substance, said solvent having a maximum vapor pressure ofless than 40 lbs. per sq. inch at sea level at a temperature of aboutF., said solvent being selected from the group consisting oftrichloromonofluoromethane, trichlorotrifluoroethane,1,1,1-trichloroethane, methylene chloride, and trichloroethylene, andfrom about 0.2 to about 0.4 part by weight of an inert gas underpressure, said inert gas being selected from the group consisting ofnitrogen, carbon dioxide, and nitrous oxide.

2. The combination of claim 1 wherein the liquid malodorous substance ismethyl mercaptan or ethyl mercaptan, the solvent istrichloromonofiuoromethane or trichlorotrifluoroethane and the inert gasis nitrogen.

References Cited UNITED STATES PATENTS 3,475,146 10/1969 Olund 252-4083,099,603 7/1963 Banker et al. 42447 OTHER REFERENCES 'Aerosol Review,1966, p. 4 and 23, TP 244.

Eckton, J. of the Soc. of Cosmetic Chemists, pp. 389 and 390, August1963, 424/47.

Herzka, 'International Encyclopedia of Pressurized Packing (aerosol),pp. 265-266 and 510, pub. 1968, by Pergamon Press, New York, N.Y., TP244.

Herzka, Pressurized Packing (aerosol), pub. 1958, pp. 93-96, QD549 H47.

DONALD LEVY, Primary Examiner US. Cl X.R.

